CN113481348A

CN113481348A - Adsorption treatment process for harmful substances in cooking pot

Info

Publication number: CN113481348A
Application number: CN202110739209.XA
Authority: CN
Inventors: 王文雄; 王绍锋; 谢泽华
Original assignee: Guangdong Murenking Appliance Co ltd
Current assignee: Guangdong Murenking Appliance Co ltd
Priority date: 2021-06-30
Filing date: 2021-06-30
Publication date: 2021-10-08
Anticipated expiration: 2041-06-30
Also published as: CN113481348B

Abstract

The application relates to the field of kitchen utensils, specifically discloses an adsorption treatment process of harmful substances in a cooking pot, which comprises the following steps: s1, preparation of an adsorbent: mixing limestone powder, aluminite powder, fluorite powder, phosphate and an adhesive to obtain an adsorbent; s2, melting: melting the pig iron blocks and the adsorbent together, and stirring to obtain molten iron, wherein the melting temperature is 1700-1850 ℃; s3, deslagging: stirring and slagging-off the molten iron; wherein the addition amount of the adsorbent is (2.5-12.0) kg/ton of pig iron block. The method has the advantages of short melting time of the pig iron blocks, good slag gathering effect and less harmful impurities in the prepared iron pan.

Description

Adsorption treatment process for harmful substances in cooking pot

Technical Field

The present application relates to the field of kitchen utensils and, more particularly, it relates to a process for the sorption treatment of harmful substances in cooking pots.

Background

The cooking pots are classified into iron pots, stainless steel pots, medical stone pots, etc. according to their materials. Wherein, the iron pan is the main kitchen ware of culinary art food, and the iron pan has the branch of raw iron pan and cooked iron pan. The pig iron pan is made by melting gray iron and pouring by a model, and has slow and uniform heat transfer, but thick pan ring and rough lines; the iron pan is made of black iron sheet by forging or manually hammering, and has the advantages of thin pan ring, rapid heat transfer and beautiful appearance.

The gray iron used in the pig iron pan contains iron-carbon alloy with carbon content of more than 2%, and in addition, the cast iron contains 1-3% of silicon and elements such as phosphorus, sulfur, lead, arsenic, antimony, mercury, vanadium, nickel, chromium, molybdenum, copper, boron and the like.

Aiming at the related technologies, the inventor thinks that the iron-carbon alloy is used for preparing the pig iron pan, the pig iron pan can be in contact with a large amount of media such as acid, alkali, salt and the like in the using process and needs to be heated to a certain temperature, substances in the pig iron pan can be separated out in the cooking process, the substances enter a human body by taking food as a medium after being separated out, the substances contain a large amount of heavy metal elements, the content of heavy metals in the human body exceeds the standard after long-term use, and the harm to the human body is great.

Disclosure of Invention

In order to reduce harmful elements separated out from an iron pan, the application provides an adsorption treatment process for harmful substances in a cooking pan.

The application provides an adsorption treatment process of harmful substances in a cooking pot, which adopts the following technical scheme:

the adsorption treatment process of harmful substances in an iron pan comprises the following steps:

s1, preparation of an adsorbent: mixing limestone powder, aluminite powder, fluorite powder, phosphate and an adhesive to obtain an adsorbent;

s2, melting: melting the pig iron blocks and the adsorbent together, and stirring to obtain molten iron, wherein the melting temperature is 1700-1850 ℃;

s3, deslagging: stirring and slagging-off the molten iron;

wherein the addition amount of the adsorbent is (2.5-12.0) kg/ton of pig iron block.

Preferably, the weight parts of the components in the adsorbent are limestone powder: an alumite powder: fluorite powder: phosphate salt: adhesive (35-60): (8-18): (18-30): (0-1.5): (0-10).

By adopting the technical scheme, the adsorbent is melted together with the pig iron blocks, the adsorbent adsorbs harmful substances such as sulfur, phosphorus, lead, arsenic, antimony, mercury and the like in a molten state in molten iron in the melting process, then the waste residues are removed by slagging off, the harmful substances in the molten iron are discharged, and the purification of the iron pan is completed. The limestone, the aluminite and the fluorite are all in an active state at a high temperature, and the limestone is decomposed at the temperature of 1700-1850 ℃ and interacts with each component of the aluminite powder and the fluorite powder to play roles of fluxing and impurity adsorption, so that the melting temperature of molten iron can be kept, and the raw iron block can be rapidly melted; and the adsorbent can gather infusible substances in the molten iron, reduce impurities in the iron pan, adsorb harmful substances in the molten iron and reduce the harmful substances in the iron pan.

Limestone can also produce carbon dioxide in the decomposition process, and can improve the molten iron mobility with fluorite combined action, improve the efficiency of edulcoration and harmful removal process.

The limestone, the aluminite and the fluorite also contain silicon-containing elements, manganese elements and other components capable of enhancing the impact resistance and the wear resistance of the iron pan, and the service life of the iron pan is prolonged; and the iron pan also contains fluorine-containing elements, magnesium elements and other components capable of supplementing trace elements for human bodies, and when the iron pan is used, the components are separated out to supplement the trace elements required by the human bodies.

Preferably, the preparation of the adsorbent comprises the following steps:

(1) crushing limestone, grinding and sieving by a 30-40-mesh sieve to obtain limestone powder, crushing and grinding aluminite and sieving by a 30-40-mesh sieve to obtain aluminite powder, crushing and grinding fluorite and sieving by a 30-40-mesh sieve to obtain fluorite powder;

(2) crushing and grinding the ascharite, sieving the ground ascharite by a 30-40-mesh sieve to obtain ascharite powder, and mixing the water glass, the zeolite particles and the ascharite powder to obtain the adhesive;

(3) uniformly mixing limestone powder, aluminite powder, fluorite powder, phosphate, an adhesive and water according to the weight ratio to obtain a mixture;

(4) and drying the mixture to obtain the adsorbent.

Preferably, the adhesive comprises the following components in parts by weight: water glass: zeolite particles ═ (1-2.5): (25-30): (6-10).

Preferably, the phosphate is sodium tripolyphosphate or sodium hexametaphosphate.

Preferably, the total adding amount of all the powder in the preparation step (3) of the adsorbent is (65-80) g/L water.

By adopting the technical scheme, the limestone, the aluminite and the fluorite after crushing and grinding can be mixed more uniformly, and the fluxing and the adsorption effect are better. The binding agent formed by mixing the boron magnesium stone, the water glass and the zeolite particles not only has good binding performance, but also can improve the dispersing performance of the limestone, the aluminite and the fluorite after being matched with the phosphate, thereby leading the dispersed limestone, the aluminite and the fluorite to be combined more firmly and more stably and leading the adsorbent to fully play the functions of fluxing and adsorption in molten iron; and an adsorbent with pores can be formed, so that the adsorption performance of the adsorbent is improved, and the adsorption effect on non-fusible impurities and harmful substances in molten iron is better; meanwhile, boron element, magnesium element, silicon element and the like can be further introduced into the iron pan,

preferably, the temperature is raised to 120 ℃ during the mixing in the preparation step (3) of the adsorbent, and the temperature is kept for 30min after the uniform mixing, wherein the temperature is kept at 110 +/-5 ℃.

By adopting the technical scheme, the mixing and combination of the water glass, the zeolite particles and the boron-magnesium stone powder can be accelerated by the temperature rise treatment, and the water glass, the zeolite particles and the boron-magnesium stone powder can keep the activity of each component by heat preservation at the temperature, so that the movement and collision among all substances in the water solution are facilitated, the components in the adsorbent are more uniformly dispersed, and the combination is tighter.

Preferably, the adsorbent is preheated before melting, the preheating temperature is 630-850 ℃, and the preheating time is 25-30 min.

By adopting the technical scheme, the preheated adsorbent is in an active state, the adsorbent can rapidly react when being melted together with the pig iron blocks, the fluxing effect is good, impurities and harmful substances in the molten iron can be adsorbed in the melting process of the pig iron blocks, the adsorption effect is good, the adsorption rate is high, the toxin expelling treatment time of the molten iron is shortened, and the energy is saved.

To sum up, the application comprises the following beneficial technical effects:

1. this application adopts the together technology of melting of adsorbent and pig iron piece, because limestone powder, aluminite powder, fluorite powder, phosphate and bonding agent mix to form the adsorbent, can accelerate the melting of pig iron piece, has improved the slag collecting efficiency of infusible impurity in the molten iron simultaneously to and adsorb the harmful impurity in the molten iron, play fluxing effect and adsorption effect.

2. The process of preheating the adsorbent is preferably adopted in the application, the components in the adsorbent enter an active state in advance after preheating, and when the adsorbent and the pig iron block are melted together, the slag gathering rate of the non-melted impurities in the molten iron and the adsorption efficiency of the harmful impurities in the molten iron can be further accelerated.

3. Through the use of adhesive and phosphate in this application, can form the adsorbent that has hole and bonding property is good, improve and gather the sediment effect, and further improve the adsorption efficiency to infusible impurity in the molten iron.

Detailed Description

The sources of the raw materials used in the examples and comparative examples of the present application are shown in the following table.

Table 1 table of sources of raw materials used in examples of the present application

Raw materials	Source	Model number
			Boron magnesium stone	Dalian jin Tuo mining Co Ltd	/
Water glass	Xian Huachang water glass Co Ltd	/
			Zeolite particles	Limited technical shares of the Beijing nation's investmentCompany(s)	/
Limestone	Guangxi Zhejiang chemical Co Ltd	/
			Alum stone	Chemical Limited Juan lan	/
Fluorite	Xinyang Xinchen mineral products Co Ltd	/

In addition to the above, other raw materials are commercially available.

Preparation example of adhesive

Preparation example 1

Crushing and grinding the ascharite, sieving the ground ascharite with 30-40 mesh sieves to obtain ascharite powder, respectively weighing 1kg of the ascharite powder, 30kg of water glass and 6kg of zeolite particles (zeolite particles with the particle size of 1-5mm are selected), putting into 20L of water, stirring and mixing uniformly at room temperature to obtain a mixture, and drying the mixture by a spray drying tower to obtain the adhesive.

Preparation examples 2 to 3 were different from preparation example 1 in the addition amounts of the boresite powder, the water glass and the zeolite particles in the binder, specifically, see table 2.

TABLE 2 EXAMPLES OF ADDITION OF THE COMPONENTS OF PREPARATIVE EXAMPLES 1-3

Preparation example 4

The difference from the preparation example 3 is that the temperature of the boron-magnesium stone powder, the water glass and the zeolite particles is raised to 100 ℃ when the boron-magnesium stone powder, the water glass and the zeolite particles are mixed uniformly, and then the temperature is kept for 30min, wherein the temperature is kept at 110 +/-5 ℃.

Preparation example 5

The difference from the preparation example 4 is that the temperature of the boron-magnesium stone powder, the water glass and the zeolite particles is increased to 120 ℃ when the boron-magnesium stone powder, the water glass and the zeolite particles are mixed uniformly, and then the temperature is kept for 30min, wherein the temperature is kept at 110 +/-5 ℃.

Preparation example 6

The difference from the preparation example 4 is that the temperature of the boron-magnesium stone powder, the water glass and the zeolite particles is raised to 80 ℃ when the boron-magnesium stone powder, the water glass and the zeolite particles are mixed uniformly, and then the temperature is kept for 30min, wherein the temperature is kept at 110 +/-5 ℃.

Preparation example 7

Preparation example 8

The difference from preparation example 3 is that the zeolite granule powder was also ground and sieved through 30 and 40 mesh sieves.

Preparation example 9

The difference from preparation example 3 is that 37.5kg of water glass was weighed in 20L of water and stirred uniformly, and then spray-dried to obtain an adhesive.

Preparation example 10

The difference from preparation example 9 is that 29kg of water glass and 8.5kg of zeolite particles were weighed and stirred in 20L of water, and then spray-dried to obtain an adhesive.

Preparation example 11

The difference from preparation example 9 is that 2.5kg of boromagnesite and 35kg of water glass are weighed and uniformly stirred in 20L of water, and then spray-dried to obtain the adhesive.

Examples of iron pan preparation

Example 1

Step 1: crushing and grinding limestone, and sieving with 30-40 mesh sieve to obtain limestone powder; crushing and grinding the aluminite; grinding, and sieving with 30-40 mesh sieve to obtain alumite powder; crushing and grinding fluorite, and sieving with 30-40 mesh sieve to obtain fluorite powder;

step 2: weighing and mixing 7kg of limestone powder, 3.2kg of aluminite powder, 6kg of fluorite powder, 0.3kg of sodium tripolyphosphate and 2kg of adhesive prepared in preparation example 1 to obtain an adsorbent;

and step 3: melting the pig iron blocks and the adsorbent together at 1700 ℃, and stirring in the melting process; wherein the addition amount of the adsorbent is 2.5 kg/ton pig iron block;

and 4, step 4: after the pig iron blocks are completely melted into molten iron, stirring and slagging off the molten iron to remove solid residues in the molten iron;

and 5: pouring the molten iron after slagging off into a die, and carrying out die casting, edge breaking and trimming to obtain the iron pan product.

Examples 2 to 3

The difference from example 1 is that the amounts of the components added in the adsorbent are different, see in particular table 3.

Table 3 table detailing the amounts of each of the components of examples 1-3 added

Example 4

The difference from example 3 is that the adhesive used in this example was the adhesive prepared in preparation example 2.

Example 5

The difference from example 3 is that the adhesive used in this example was the adhesive prepared in preparation example 3.

Example 6

The difference from example 3 is that the adhesive used in this example was the adhesive prepared in preparation example 4.

Example 7

The difference from example 3 is that the adhesive used in this example was the adhesive prepared in preparation example 5.

Example 8

The difference from example 3 is that the adhesive used in this example was the adhesive prepared in preparation example 6.

Example 9

The difference from example 3 is that the adhesive used in this example was the adhesive prepared in preparation example 7.

Example 10

The difference from example 3 is that the adhesive used in this example was the adhesive prepared in preparation example 8.

Example 11

The difference from example 3 is that the adhesive used in this example was the adhesive prepared in preparation example 9.

Example 12

The difference from example 3 is that the adhesive used in this example was the adhesive prepared in preparation example 10.

Example 13

The difference from example 3 is that the adhesive used in this example was the adhesive prepared in preparation example 11.

Example 14

The difference from example 3 was that 9.16kg of limestone powder, 3kg of aluminite powder, 4.6kg of fluorite powder, and 1.6kg of the binder prepared in production example 1 were weighed and mixed to obtain an adsorbent.

Example 15

The difference from example 3 is that 10kg of limestone powder, 3kg of aluminite powder, 5.2kg of fluorite powder and 0.16kg of sodium tripolyphosphate were weighed and mixed to obtain an adsorbent.

Example 16

The difference from example 3 is that the phosphate used in this example is sodium hexametaphosphate.

Example 17

The difference from example 3 is that the melting temperature of the pig iron nuggets and the adsorbent in step 3 was 1730 ℃.

Example 18

The difference from example 3 is that the melting temperature of the pig iron nuggets and the adsorbent in step 3 was 1760 ℃.

Example 19

The difference from example 3 is that the melting temperature of the pig iron nuggets and the adsorbent in step 3 was 1830 ℃.

Example 20

The difference from example 3 was that the amount of the adsorbent added was 5.0 kg/ton of pig iron nuggets.

Example 21

The difference from example 3 was that the amount of the adsorbent added was 8.5 kg/ton of pig iron nuggets.

Example 22

The difference from example 3 was that the amount of the adsorbent added was 12.0 kg/ton of pig iron nuggets.

Example 23

The difference from the embodiment 3 is that a preheating step is further included between the step 2 and the step 3, the preheating temperature of the adsorbent is 630 ℃, and the preheating time is 30 min.

Example 24

The difference from example 21 is that the preheating temperature of the adsorbent was 720 ℃ and the preheating time was 28 ℃.

Example 25

The difference from example 21 is that the preheating temperature of the adsorbent was 850 ℃ and the preheating time was 25 ℃.

Comparative example

Comparative example 1

And melting the pig iron blocks at 1700 ℃, stirring in the melting process, stirring and slagging off the molten iron after the pig iron blocks are completely melted into the molten iron, removing solid residues in the molten iron, pouring the slagging-off molten iron into a mold completely consistent with the mold used in the embodiment 1, and carrying out die casting, edge breaking and trimming to obtain the iron pan product.

Comparative examples 2 to 7

The difference from example 3 is that the amounts of the components added in the adsorbent are different, see in particular table 4.

TABLE 4 addition levels of components in the adsorbents of comparative examples 2-7 are detailed

Comparative example 8

The difference from example 3 was that the amount of the adsorbent added was 1.0 kg/ton of pig iron nuggets.

Comparative example 9

The difference from example 3 is that, in step 3: first, limestone powder and pig iron nuggets in amounts equivalent to those in the adsorbent composition of example 3 were melted, and then, alunite powder, fluorite powder, phosphate, and a binder in amounts equivalent to those in the adsorbent composition of example 3 were added to molten iron in this order, melted, and stirred.

Comparative example 10

The difference from example 3 is that, in step 3: melting the pig iron blocks at 1700 ℃; after the pig iron blocks are completely melted into molten iron, adding the adsorbent into the molten iron, and continuing stirring.

Performance test method

The iron pans prepared in the above examples and comparative examples were subjected to a migration test using GB4806.9-2016, and the content of heavy metals precipitated during the use of the iron pans was determined.

Preparing 1g/L citric acid solution: 1.09g of citric acid monohydrate (C) was weighed₆H₈O₇·H₂O), adding water to dissolve to 1000 mL. The water used in the method is primary water specified in GB/T6682.

The iron pots prepared in examples 1 to 25 were numbered as samples 1 to 25; the iron pots prepared in comparative examples 1 to 10 were numbered as samples 26 to 35.

And (3) detecting heavy metal ions separated out from the samples 1-35: pouring 1g/L of citric acid solution into an iron pan, wherein the addition amount of the citric acid solution is about 4/5 of the volume of the iron pan, boiling for 1h, and then measuring the content of heavy metals in the citric acid solution to be used as the precipitation amount of the heavy metals in the iron pan.

The migration amounts of arsenic, cadmium, chromium, lead, nickel, antimony and zinc in the iron pan precipitation amount were measured by inductively coupled plasma mass spectrometry in GB31604.49-2016, and the specific measurement results are shown in table 5.

(II)

The molten iron generation and slag removal time measurement: the charging time of the pig iron blocks in examples and comparative examples was t₀The time for completion of slag skimming is t₁And measuring the melting and slagging-off time t ═ t of the molten iron₁-t₀) h. Specific measurement results are shown in table 5.

TABLE 5 migration amounts of As, Cd, Cr, Pb, Ni, Sb and Zn in the iron pan precipitation amount

Molten iron generation and slag removal time measurement

Note: the units of the test results of the arsenic, the cadmium, the chromium, the lead, the nickel, the antimony and the zinc are all (mu g/L).

The iron pan can be used as a frying and frying cooking pan in daily life, and the national food safety standard GB31604.49-2016 limits the migration amount of heavy metals such as arsenic, cadmium, chromium, lead, nickel, antimony, zinc and the like precipitated in the use process of the iron pan, and specifically refers to Table 6.

TABLE 6 migration indexes of As, Cd, Cr, Pb, Ni, Sb and Zn in food contact materials and products

Element(s)	Detection limit	Limit of quantification
			Arsenic (As)/(μ g/L)	0.2	0.6
Cadmium (Cd)/(μ g/L)	0.1	0.3
			Chromium (Cr)/(μ g/L)	1	3
Lead (Pb)/(μ g/L)	0.3	0.9
			Nickel (Ni)/(μ g/L)	0.3	0.8
Antimony (Sb)/(μ g/L)	0.03	0.1
			Zinc (Zn)/(mu g/L)	0.2	0.6

Note: when the measurement result is less than the detection limit, the report is 'undetected'; when the measurement result is less than the quantitative limit, "pass", and a specific detection value is reported.

By combining the data in the detection report tables 5 and 6 of the samples 1 to 25, the migration amounts of heavy metals such as arsenic, cadmium, chromium, lead, nickel, antimony, zinc and the like in the iron pan treated by the method meet the requirements of national standards in the use process.

The data of the detection report table 5 of the samples 1 to 35 are combined, so that the sum of the melting time and the slag skimming time of the pig iron blocks treated by the scheme is reduced, namely, the addition of the adsorbent can achieve the effect of fluxing agent on the melting of the pig iron blocks, the melting time of the pig iron blocks is shortened, the production efficiency is improved, and the energy is saved.

Combining the data of the samples 1-25 and 26, it can be seen that the migration amounts of the heavy metals such as arsenic, cadmium, chromium, lead, nickel, antimony, zinc and the like in the sample 26 are all higher than the national food safety standard and do not meet the requirements of the national standard, while the migration amounts of the heavy metals such as arsenic, cadmium, chromium, lead, nickel, antimony, zinc and the like in the iron pan after the detoxification treatment by the adsorbent meet the requirements of the national standard. Therefore, the content of heavy metals such as arsenic, cadmium, chromium, lead, nickel, antimony, zinc and the like in the iron pan treated by the adsorbent after detoxification is reduced, the heavy metal precipitation rate is low in the daily use process of the iron pan, the problem that the heavy metal content ingested by a human body is excessive and influences the health of the human body is solved, and the requirement of a consumer on using the iron pan for a long time can be met.

According to the data of the sample 3 and the samples 27-32, the components in the adsorbent are combined by limestone, aluminite and fluorite, so that the adsorption effect on impurities in molten iron is good, the content of heavy metal in an iron pan is reduced, and the precipitation of heavy metal elements in the use process of the iron pan can be reduced; and the fluxing effect is good, the production time can be shortened, the energy can be saved, and the production cost can be reduced.

As can be seen by combining the data of examples 23-25 and example 3, the adsorbent had better adsorption effect after the preheating treatment; it can be seen from the data of examples 11 to 13 that the binder composed of the ludwigite, the water glass and the zeolite particles has good slag conglomeration effect, not only can shorten the slag removing time of the pig iron blocks, but also can further reduce the heavy metal content in the molten iron, and further improve the use safety and the service life of the iron pan.

The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.

Claims

1. The adsorption treatment process of harmful substances in the cooking pot is characterized by comprising the following steps of:

s3, deslagging: stirring and slagging-off the molten iron;

2. The adsorption treatment process of harmful substances in a cooking pan according to claim 1, wherein the preparation of the adsorbent comprises the steps of:

(4) and drying the mixture to obtain the adsorbent.

3. The process for adsorbing and treating harmful substances in a cooking pot as claimed in claim 2, wherein the total addition amount of all powders in the step (3) of preparing the adsorbent is (65-80) g/l water.

4. The process for adsorbing and treating harmful substances in a cooking pot as claimed in claim 2, wherein the temperature of the adsorbent in the step (3) is increased to 100 ℃ and 120 ℃ during mixing, and the temperature is maintained for 30min after mixing, wherein the temperature is maintained at 110 ± 5 ℃.

5. The process of claim 2, wherein the adhesive comprises the following components in parts by weight: water glass: zeolite particles = (1-2.5): (25-30): (6-10).

6. The process of claim 1, wherein the adsorbent comprises limestone powder as the following components in parts by weight: an alumite powder: fluorite powder: phosphate salt: adhesive = (35-60): (8-18): (18-30): (0-1.5): (0-10).

7. The process for the sorption treatment of harmful substances in a cooking pot according to claim 1, wherein the phosphate is sodium tripolyphosphate or sodium hexametaphosphate.

8. The process for adsorbing and treating harmful substances in a cooking pot as claimed in claim 1, wherein the adsorbent is preheated before melting at a temperature of 630-850 ℃ for 25-30 min.